WO2017104759A1 - Tablet-type freeze-dried cosmetic - Google Patents

Abstract

A tablet-type cosmetic excellent in handleability is provided. The tablet-type cosmetic according to the present invention contains (A) 10-20% by mass of trehalose and (B) 0.5-3.0% by mass of polyethylene glycol having a molecular weight of 2,500-20,000, and has a bulk specific gravity of 0.1-0.5 g/ml.

Description

Tablet-type freeze-dried cosmetics Related applications

This application claims the priority of Japanese Patent Application No. 2015-245470 filed on December 16, 2015, and is incorporated herein.

The present invention relates to tablet-type freeze-dried cosmetics, and more particularly to the improvement of handling ease as a tablet.

Usually, highly functional skin care cosmetics containing active ingredients are provided mainly in the form of liquids such as skin lotions and cosmetic liquids, and their effects are exhibited by daily habitual use.
On the other hand, in recent years, there are increasing opportunities for skin care to be performed at travel destinations, business trip destinations, sports gyms, and the like, and therefore, products that have less burden when being carried are required. Furthermore, with the recent improvement in beauty consciousness, there is a demand for high-quality products that can achieve a level of satisfaction equivalent to or better than daily care for skin care cosmetics used on the go.
In addition, not only for portable use as described above, but also for skin care cosmetics that are used on a daily basis or according to the skin condition, there is a high demand for products that can be used easily and customized.

As one of means for satisfying the above requirements, a form in which a liquid composition such as a skin lotion is used as a dry preparation, which is redissolved in water at the time of use can be considered.
For example, Patent Document 1 discloses L-ascorbic acid-2-phosphate, which is unstable in the presence of water, sugar alcohol, oligosaccharide having low hygroscopicity, and a technique relating to dry formulation of a liquid composition. It is described that an aqueous solution mixed with a water-soluble polymer can be kept stable until use by lyophilization.
Patent Document 2 discloses that a freeze-dried cosmetic obtained by freeze-drying an aqueous solution containing sodium hyaluronate, collagen, and an ascorbic acid derivative shrinks or cracks due to moisture absorption, bacteria and oxidation even after long-term storage. It is described that it dissolves in a very short time when it is redissolved with water or lotion during use.
Patent Document 3 describes that a hyaluronic acid solid composition stable at room temperature was obtained by freeze-drying an aqueous solution containing sodium hyaluronate and a saccharide.
Also in Patent Document 4, a powder or granular cosmetic using a freeze-dried product of an aqueous solution containing hyaluronic acid or sodium hyaluronate and phosphoric acid-L-ascorbyl magnesium exhibits the solubility of both components in water. It is described to improve.

JP 2004-149468 A JP 2006-182750 A JP 2003-95955 A JP-A-2-215707

However, the freeze-dried compositions taught in Patent Documents 1 to 4 are not sufficient in terms of peelability from a container or the like, re-solubility, and feeling of use of the re-dissolved liquid as a molded tablet-shaped freeze-dried product. It has been difficult to produce tablet-type cosmetics that are highly portable and can be used easily. In particular, a technique relating to a tablet that has a low hygroscopicity during storage but dissolves instantly when water is added is not yet known.
This invention is made | formed in view of the said situation, and it aims at providing the tablet type freeze-drying cosmetics excellent in the ease of handling.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention, comprising a polyethylene glycol of specific molecular weight and trehalose, and a composition formed into a tablet shape by freeze-drying so as to have a specific bulk specific gravity, The present invention was completed by finding that it dissolves instantly by addition of water despite its low hygroscopicity, has high releasability, and is easy to handle.
That is, the tablet-type freeze-dried cosmetic according to the present invention is
(A) 10-20% by mass of trehalose,
(B) 0.5 to 3.0% by mass of polyethylene glycol having a number average molecular weight of 2500 to 20000,
And having a bulk specific gravity of 0.1 to 0.5 g / ml.
In the cosmetic, (B) preferably contains polyethylene glycol having a number average molecular weight of 15000 to 20000.
The cosmetic preferably comprises (C) hyaluronic acid and (D) a thickener.
In the cosmetic, it is preferable that the blending amount of (C) hyaluronic acid is 0.01 to 1% by mass.
In the cosmetic, it is preferable that the blending amount of (D) thickener is 0.01 to 0.5% by mass.
In the cosmetic, (D) the thickener is preferably selected from xanthan gum, tamarind gum, sodium alginate, gellan gum, agar, polyvinyl alcohol, carboxyvinyl polymer, and quince seed.

ADVANTAGE OF THE INVENTION According to this invention, the tablet-type freeze-dried cosmetics applied to the skin etc. which can be melt | dissolved instantly by adding a small amount of water by the combination of a trehalose and the polyethylene glycol of a specific number average molecular weight are obtained. Further, the tablet-type cosmetics have very little moisture absorption, and can provide cosmetics with portability and ease.
Furthermore, when hyaluronic acid and a thickener are blended, a tablet-type freeze-dried cosmetic with excellent usability can be obtained.

Hereinafter, the present invention will be described in detail.
The tablet-type freeze-dried cosmetic according to the present invention contains trehalose and polyethylene glycol having a specific number average molecular weight, and is basically produced by volatilizing a medium from a uniform solution / dispersion solution of the components. It is. First, the components of the present invention will be described.

<Excipient>
Ingredients blended as an excipient in the present invention are (A) trehalose and (B) polyethylene glycol.

(A) Trehalose (A) Trehalose used in the present invention is a disaccharide in which two D-glucoses are linked, and the binding mode is α, α-, α, β-, β, β- There are three types, and α, α-binding modes that are found in large numbers in nature are common.

Trehalose, a type of sugar, has strong water retention, and is superior in terms of stability, resolubility and releasability as a freeze-dried cosmetic compared to sugars such as erythritol, xylitol, and sorbitol. Yes.

The amount of trehalose is preferably 10 to 20% by mass. Further, the content of 15 to 20% by mass is more preferable from the viewpoint of excellent high temperature stability. If it is less than 10% by mass, it is not preferable in that the stability at high temperatures and the solubility in water during re-dissolution may be insufficient. On the other hand, if it exceeds 20% by mass, the high temperature resistance is excellent, it is difficult to freeze, there is a case where bumping may occur, and it is not preferable from the viewpoint of usability.

Examples of commercially available trehalose include trehalose (for cosmetics) (manufactured by Hayashibara Co., Ltd.).

In addition to trehalose, other saccharides can be added as long as the effects of the present invention are not lost.
For example, maltose, maltotetraose, maltosyl trehalose and the like can be mentioned.

(B) Polyethylene glycol (B) Polyethylene glycol used in the present invention includes those having a number average molecular weight of 2500 to 20000 from the viewpoint of tablet formability. More preferably, it is preferably 15000 to 20000 in terms of moldability and releasability.
When the number average molecular weight is less than 2500, it is not preferable in that the releasability may be deteriorated. Moreover, when the number average molecular weight is larger than 20000, it is not preferable in that re-solubility is poor and feeling in use may be inferior.

The blending amount of (B) polyethylene glycol is preferably 0.5 to 5% by mass, more preferably 0.5 to 3%, and further preferably 1 to 2% by mass with respect to the pre-lyophilization solution of the present invention. is there. When it mixes exceeding 5 mass%, the mold release property and usability of a tablet may fall.

Moreover, the said polyethylene glycol may use what was synthesize | combined by the well-known synthesis | combining method, or may use a commercial item.
Examples of commercially available polyethylene glycol include PEG-20000 (manufactured by Sanyo Chemical Industries, Ltd.).

(C) Hyaluronic acid (C) Hyaluronic acid used in the present invention is a linear polymer in which N-acetyl-D-glucosamine residues and D-glucuronic acid residues are alternately bonded. What was processed into the powder form etc. can be used.

The hyaluronic acid can be obtained by, for example, isolation and extraction from a chicken crown or other animal tissues, or a fermentation method using a microorganism such as Streptococcus. Further, in the present invention, for example, as a derivative of hyaluronic acid, a hyaluronic acid metal salt such as hyaluronic acid sodium salt and hyaluronic acid potassium salt, and a hydroxyl group and a carboxyl group of hyaluronic acid are etherified, esterified and amidated. Alternatively, powders such as hyaluronic acid derivatives obtained by acetylation, acetalization, and ketalization may be used.
Moreover, a commercial item can also be used as hyaluronic acid. Examples of commercially available hyaluronic acid include hyaluronic acid HA-LQ (manufactured by Kewpie Fine Chemical), hyaluronic acid FCH (manufactured by Kikkoman Biochemifa Co., Ltd.), and the like.

The molecular weight of (C) hyaluronic acid is not particularly limited, but it is preferable that the molecular weight is 100,000 or more, and the molecular weight is about 500,000 to 3,000,000. When hyaluronic acid having a low molecular weight of less than 100,000 is used, the formability to tablets and the feeling of use after re-dissolution may not be sufficient. On the other hand, if the molecular weight is larger than 3 million, it is not preferable in that the solubility and the feeling of use after re-dissolution may be insufficient.

Among the above excipients, (C) hyaluronic acid, in particular, exhibits extremely high viscosity even in the state of a low concentration aqueous solution, so its blending amount is related to the properties of the lyophilized tablet and its redissolved solution. Is expensive.
The blending amount of (C) hyaluronic acid is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.2% by mass with respect to the pre-lyophilized solution of the present invention. If it exceeds 1% by mass, the solubility and releasability of the tablet will decrease, which is not preferable.

(D) Thickener The (D) thickener used for this invention is used in order to improve the moldability and mold release property of tablet cosmetics.
(D) As a thickener, water-soluble polymers such as xanthan gum, tamarind gum, sodium alginate, gellan gum, agar, polyvinyl alcohol, carboxyvinyl polymer, and quince seed can be used. Among these, it is preferable to use xanthan gum, tamarind gum, and quince seed in terms of using a tablet cosmetic and having less stickiness when dry, and less stickiness.

(D) The blending amount of the thickener is preferably 0.01 to 0.5% by mass, more preferably 0.05 to 0.1% by mass, based on the pre-lyophilized solution of the present invention. If it exceeds 0.5% by mass, the releasability and usability of the tablet may decrease, and if the amount is less than 0.01% by mass, the moldability and releasability may decrease. is there.

Examples of such commercially available thickeners include xanthan gum (Celtrol, manufactured by Kelco), tamarind gum (Glyloid 6C, manufactured by Dainippon Pharmaceutical Co., Ltd.), sodium alginate (Duck Algin NSPH, Kikkoman Biochemifa Corporation). ), Gellan gum (Kelcogel, DSP Gokyo Food & Chemical Co., Ltd.), agar (Inagar CS-110, Ina Food Industry Co., Ltd.), and the like.

In addition to the above components, the tablet-type freeze-dried cosmetic composition according to the present invention may contain other components that can be added to normal cosmetics and quasi-drugs as long as the effects of the present invention are not impaired. .
In the production of the present invention, the use of an aqueous component is particularly preferable as the other component, but an oily component can be blended by solubilization using a surfactant or the like.
Examples of the aqueous component include polyhydric alcohols, water-soluble polymers other than the component (D), chelating agents, pH adjusters, preservatives, and the like.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerol, polyethylene glycol having a molecular weight other than those described above, polyglycerol, and the like.

Examples of water-soluble polymers include those other than those described above, for example, hydrophilic synthetic polymers such as polyacrylic acid, polyethylene glycol, polyacrylamide, polyalkylacrylamide / polyacrylamide copolymer, carboxymethylcellulose, cationized cellulose, pluronic, macrogol. , Popidone, polyvinyl methacrylate, polyethyleneimine and the like; hydrophilic natural polymers such as succinoglycan, guar gum, locust bean gum, curdlan, alginic acid, carrageenan, mannan, pectin, gum arabic, karaya gum, casein, α-cyclodextrin, Dextrin, dextran, gelatin, collagen, pectin, starch, chitin and its derivatives, chitosan and its derivatives, elastin, heparin, heparan Acid, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose; as a hydrophilic clay mineral, laponite, bentonite, smectite, and the like.

Examples of the chelating agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, tetrasodium edetate, Examples include sodium acid, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, and trisodium ethylenediaminehydroxyethyl triacetate.

Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

Examples of the preservative include paraoxybenzoic acid ester and phenoxyethanol.

In addition, examples of the oil component include fragrances and oil-based drugs (for example, vitamin A).

Other ingredients that can be added include, for example, humectants (eg, 2-methacryloyloxyethyl phosphorylcholine (MPC) copolymer, PEG / PPG dimethyl ether such as PEG / PPG-14 / 7 dimethyl ether), water-soluble collagen, hydrogen peroxide treatment Yeast hydrolysate, sodium dl-prolidonecarboxylate, L-hydroxyproline, calcium chloride, magnesium chloride); various extracts (eg, rose, apricot, auren, sicon, peonies, assembly, birch, sage, loquat, carrot , Aloe, mallow, iris, grape, yokuinin, loofah, lily, saffron, senkyo, ginger, hypericum, onionis, garlic, capsicum, chimpi, cypress, seaweed, etc.); other water-soluble drugs (eg, tranexamic acid), etc. The active ingredient and the like, can be added the desired effect in the cosmetic of the present invention these formulations.
In addition, the thickener and trehalose which are essential components can also provide a moisturizing effect in the present invention.

The tablet-type cosmetics according to the present invention can be obtained as a dry product that remains after dissolving or dispersing the above-described blended components in a volatile liquid medium such as water or lower alcohol, and sublimating by freezing after freezing.
In the manufacture of the tablet-type cosmetic according to the present invention, the excipient component dissolved in a medium such as water forms a three-dimensional network structure in the medium. If only the medium is removed from such a state, the network structure shrinks due to drying, and is distorted or collapsed. Therefore, it is usually difficult to maintain the structure. However, in the present invention, trehalose blended with the excipient supports the network structure instead of the medium even after volatilization of the medium, so that it is considered that the structure by the excipient is almost maintained.

In addition, the dried product in which the three-dimensional network structure of the excipient is maintained is in a porous state in which the medium portion has been removed from the structure. When water is added during re-dissolution, water is introduced into the network structure from each hole. Penetration and dissolution of the entire tablet formulation proceeds. At that time, the higher the density of the constituents including the structure, the more difficult the water penetrates into the interior, and the formulation becomes less soluble. On the other hand, if the density of the constituent components is too low, the preparation itself is fragile and easily collapses, and it is easy to absorb moisture during storage.
For this reason, in order to make a formulation that has extremely low hygroscopicity during storage, while having a solubility that allows water to permeate and disintegrate instantaneously, the bulk density of the constituents is further set within a certain range. There is a need.

Therefore, the tablet cosmetic according to the present invention contains the above-described constituents and has a bulk specific gravity of 0.1 to 0.5 g / ml, preferably 0.15 to 0.3 g / ml. Cost.
If the bulk specific gravity is less than 0.1 g / ml, the hygroscopicity during storage increases, and if it exceeds 0.5 g / ml, the solubility in water tends to decrease. On the other hand, if the bulk specific gravity is within the above range, the number of holes through which the medium has escaped is moderately large, and the network structure of the thickener is also fixed in a moderately widened state. In this case, the solubility is extremely good.

As a method for measuring the bulk specific gravity, the tablet weight after freeze-drying (g) ÷ freeze-drying type volume (ml) is calculated.

The tablet-type cosmetic according to the present invention is, for example, filled in a tablet mold with a solution in which constituent components are dissolved or dispersed in a volatile liquid medium such as water or lower alcohol, and then freeze-dried. It can manufacture by taking out from.
The present invention can be molded into any size and shape by setting the volume of the preparation, the components and the amount of the medium so as to satisfy the above-mentioned bulk specific gravity.
However, an extremely thin shape or an excessively complicated shape is not preferable because there is a problem in moldability.
Further, the present invention has a low hygroscopic property of the preparation, and has a high releasability and is easily peeled from the container. Therefore, the present invention is not limited to a form (for example, blister pack) packaged for each used portion while being filled in the container. Only the preparation removed from the mold) can be packaged in any form.

The tablet-type cosmetics according to the present invention can usually be used by adding an appropriate amount of water to redissolve the preparation and applying the solution to the skin or the like. The amount of water to be added should be adjusted so that the viscosity is easy to apply, with the lower limit of the complete dissolution of the preparation, but if it is too much, the component concentration is too low to obtain a sufficient effect. Yes, if it is too little, it may become sticky at the time of application. Therefore, although not particularly limited, it is preferable to adjust the addition amount to about 1 to 10 times the volume of the preparation.
The place where water is added to the preparation may be on the palm, on the application site, or in a suitable container. However, as a method of using the present invention, the preparation for one-time use is placed on the palm. After adding water, it is preferable to apply the solution on the palm as it is to the application site by hand.
Note that lotion or the like may be used instead of water as long as the formulation can be redissolved.

The tablet-type cosmetic according to the present invention may be in any product form, such as lotion, cosmetic liquid, pack, cleansing, facial cleansing foam, hand cream, shampoo, rinse, hair treatment, sunscreen, etc., depending on the ingredients to be blended. In particular, it is suitable for use as a moisturizing lotion or cosmetic liquid.

EXAMPLES Hereinafter, although an Example is given and this invention is explained in full detail, this invention is not limited at all by these. Unless otherwise specified, the blending amount is expressed in mass% with respect to the system in which the component is blended.
First, the evaluation method and evaluation criteria used in the following tests will be described.

<Solubility>
Each test example composition (about 100 mg) was placed on the palm, 500 μl of water was dropped, and the time required for the formulation to dissolve completely was evaluated according to the following criteria.
A: The preparation completely dissolved instantly.
B: The preparation required a little time but dissolved completely.
C: The preparation was slightly difficult to dissolve, and a part of the undissolved part was generated.
D: The preparation was difficult to dissolve and a residue was left undissolved.
E: The preparation did not dissolve.

<Usability>
Each test example composition (about 100 mg) is placed on the palm, added with 500 μl of water, dissolved and applied to the skin (moistness, non-stickiness, smoothness of the skin) by 10 experts The panel evaluated as follows.
A: 6 or more out of 10 responded that the feeling of use was good.
B: 3 or more and less than 6 out of 10 responded that the feeling of use was good.
C: Less than 3 out of 10 responded that the feeling of use was good.

<Releasability>
After the drying step in the production method of each test example composition, the ease with which the dried product was taken out from the container was evaluated according to the following criteria.
A: The formulation was very easily removed from the container.
B: The formulation was easily removed from the container.
C: The preparation was slightly difficult to leave from the container.
D: The preparation was very difficult to leave from the container.

<Moldability>
The moldability after the drying step in the production method of each test example composition was evaluated according to the following criteria.
A: The preparation was molded from the container according to the mold.
B: The preparation was molded from the container almost according to the mold.
C: The preparation was molded with small cracks from the container.
D: The product was not molded according to the mold, for example, the formulation became smaller from the container.
E: The preparation had a large crack from the container or a brittle crack.

The test example compositions of the formulations described in the following tables were prepared according to the following production methods.
<Manufacturing method>
Various compounding ingredients were dissolved or dispersed in a volatile liquid medium such as water or lower alcohol, poured into a mold, sublimed by freezing after freezing, and a tablet-type freeze-dried cosmetic was obtained as a dry product remaining later.

First, this inventor examined the moldability of the tablet cosmetics about the saccharide | sugar used as an excipient | filler.
The prescriptions for the test examples listed in Table 1 below are as follows.

Ion-exchanged water Remaining sugars Total amount shown in Table 1 100%

From this, it was found that, as the basic skeleton of the excipient, trehalose is excellent in terms of moldability among sugars.
Therefore, the inventor examined the blending amount of trehalose in the following.

As can be seen from Test Examples 2-1 to 2-6, if the amount of trehalose exceeds 20% by mass, bumping occurs, which is not preferable from the viewpoint of moldability. Moreover, as re-solubility, when the compounding quantity of trehalose exceeds 20 mass%, since there exists undissolved, it is unpreferable.

Therefore, the present inventor examined whether or not moldability and releasability could be improved by adding (B) polyethylene glycol as another component.

(* 1) Trehalose; Hayashibara Co., Ltd.

As can be seen from Test Examples 3-1 and 3-2, it was found that when (B) polyethylene glycol was added, an excipient excellent in moldability and releasability was obtained while maintaining re-solubility.

The present inventor further examined the usability as a tablet cosmetic.

(* 3) Bio Hiaro 12; manufactured by Shiseido Co., Ltd. (* 4) Glyroid 6C; manufactured by Dainippon Pharmaceutical Co., Ltd. (* 5) Lipdure-PMB (Ph10); manufactured by NOF Corporation

From Table 4 and Table 5, in order to improve the usability, (B) while blending polyethylene glycol, by further adding a moisturizing agent and a thickening agent, moldability, releasability, re-dissolvability It was found that the usability can be improved while maintaining.

Next, the number average molecular weight of the blended (B) polyethylene glycol was examined.

From Test Examples 6-1 to 6-7, the polyethylene glycol (B) preferably has a number average molecular weight of 4,000 to 20,000 in terms of moldability and usability.

* Ethanol was used as alcohol.

* Ethanol was used as alcohol.

Test Examples 7-1 to 7-6 were tablet cosmetics excellent in re-dissolvability and usability, and excellent in high-temperature stability.

The formulation example of the tablet-type freeze-dried cosmetic (detergent) of the present invention is as follows.

The formulation example of the tablet-type freeze-dried cosmetic (hair treatment) of the present invention is as follows.

The formulation example of the tablet-type freeze-dried cosmetic (shampoo) of the present invention is as follows.

Formulation examples 4 to 7 of the tablet-type freeze-dried cosmetic (cosmetic for skin application) of the present invention are as follows.

Claims (6)

1. (A) 10-20% by mass of trehalose,
   (B) 0.5 to 3.0% by mass of polyethylene glycol having a number average molecular weight of 2500 to 20000,
   And a tablet-type freeze-dried cosmetic characterized by having a bulk specific gravity of 0.1 to 0.5 g / ml.
2. 2. The tablet-type freeze-dried cosmetic according to claim 1, wherein (B) comprises polyethylene glycol having a number average molecular weight of 15000 to 20000.
3. 3. The tablet-type freeze-dried cosmetic according to claim 1, wherein the cosmetic comprises (C) hyaluronic acid and (D) a thickener.
4. The tablet-type freeze-dried cosmetic according to any one of claims 1 to 3, wherein the blending amount of (C) hyaluronic acid is 0.01 to 1% by mass.
5. 5. The tablet-type freeze-dried cosmetic according to claim 4, wherein the blending amount of (D) thickener is 0.01 to 0.5% by mass.
6. The cosmetic according to any one of claims 3 to 5, wherein (D) the thickener is selected from xanthan gum, tamarind gum, sodium alginate, gellan gum, agar, polyvinyl alcohol, carboxyvinyl polymer, and quince seed. A tablet-type freeze-dried cosmetic.